Stable fuel compositions



3,h7,785 Patented Nov. 7, 1961 9 Claims. (Cl. 44-75) This inventionrelates to stabilized distillate fuel oils. More particularly, theinvention is concerned with the stabilization of distillate fuel oilscontaining a m xture of straight run and catalytically cracked fuel oildistillates by incorporation therein of the herein disclosed noveladducts.

Distillate fuel oil compositions containing mixed straight run andcatalytically cracked fuel oil distillates have proved exceptionallytroublesome with regard to sludge deposition during storage at normalatmospheric temperatures. It has been found that the sludgingcharacteristics of such mixed, or blended, fuel oil distillates arestrikingly poor, much poorer than can be accounted for from the knownsludging characteristics of the individual component fuel oildistillates alone. Although the exact cause for the unusual instabilityof mixed distillate fuel oils is not fully understood, the unusualcharacter and the unexpectedly large volume of sludge formed by suchmixed distillate fuel oils have led those skilled in the ant to regardthe problem of sludge deposition in mixed distillate fuel oils asseparate and distinct from that of sludging or solids deposition inother oils.

More particularly, straight run distillate fuel o'ds containpredominantly parafiinc components. Sludge deposition in these oils,where such occurs, is considered to result from the presence of minoramounts of components that are not normally present and which impartinstability to the otherwise stable oil, e.g., impurities picked upduring refining, rather than from the inherent instability of thehydrocarbon components of the oil. The problem of sludge formation insuch oils is considered essentially one involving oxidation and theformation of insoluble oxygenated products.

Catalytically cracked fuel oil distillates on the other hand are rich inolefinic, aromatic and mixed olefinicaromatic compounds. iSludging insuch oils is considered to involve primarily condensation and/orpolymerization type reactions which result in the formation of insolublereaction products of relatively high molecular weight.

Still furthensludge deposition in blends of straight run andcatalytically cracked fuel oil distillates is an entirely distinctproblem from that for either component oil. While the sludge formed insuch blended fuel oils very probably contains some sludge of the typeformed in each component oil, the sludge formed in blended fuel :oils isconsistently greatly in excess of the amount that can be accounted forfrom the known sludging tendencies of the individual component oils,thus indicating the existence of a special problem.

The problem of sludge deposition in mixed straight run and catalyticallycracked fuel oil distillates is not only distinct from that of sludgedeposition in individual fuel oil distillates, but also from that ofsludge deposition in lubricating oils and from that of gum formation ingasolines. In the former instance sludge formation is attributed to thehigh temperature oxidation of the highly paraifinic components containedin the oil, the reaction of acidic oxygenated products with metalscontacted reaction may be carried out at any temperature betweentherewith, and, in the case of crankcase lubricants, sludge formation isadditionally attributed to the presence of foreign materials such aswater, dust particles, carbon, incompletely burned fuel and the like.

Gum formation in gasolines on the other hand is attributed primarily tothe oxidation of olefinic linkages (as opposed to oxidation ofparafiinic compounds). Moreover, the gums formed in gasoline are notnormally insoluble in the gasoline as is the case with sludge; instead,deposition of gums from gasoline occurs upon vaporization of the latter,rather than during storage as is the case with blended fuel oils.

We have found that sludge deposition in mixed catalytically cracked andstraight run fuel oil distillates can be substantially diminished byincorporation therein of small amounts of the novel adduots disclosedherein. The adducts whose use is included by this invention are thereaction products formed by the substantially spontaneous reaction of aphenolic compound and a 1,3-diaminopropane having the following generalformula:

where R is an aliphatic radical containing from 8 to 30 carbon atoms,and where the mol ratio of reactants is from about 0.5 to about 1 mol ofthe 1,3-diaminopropane per equivalent weight of phenolic compound.

The adducts disclosed herein are prepared by reaction of a phenoliccompound with a 1,3-diaminopropane that contains a long-chain aliphaticradical-substituted, secondary amino grouping. The aforesaid reactiontakes place substantially spontaneously at room temperature. In mostcases evolution of heat is observed, but in some cases the reaction hasbeen observed to occur with the adsorption of heat. Although even theendothermic reactions take place spontaneously at room temperature, inthe case of strongly endothermic reactions, or in the case of highlyviscous reactants, the reaction may be caused to take placesubstantially spontaneously with the application of moderate heat. Theterm substantially spontaneously as used herein is meant to include notonly spontaneous reactions but also those in which moderate heating isutilized to accelerate and/or insure completion of the reaction. Subjectto the foregoing qualification, and provided that the decompositiontemperatures of the reactants and the reaction products are notexceeded, the

about 10 and about C. In order to produce the desired reaction products,the ratio of the reactants in the reaction mixture should be from about0.5 to about 1 mol of the 1,3-diaminopropane per equivalent weight ofphenolic compound. The terms mol and equivalent Weight are used in theirconventional sense herein. Thus, the term mol is used to denote agram-molecular weight, while the term equivalent weight, as applied tothe phenolic compounds, is used to denote that amount that would furnishone gram-ionic weight of hydrogen ion, if the compound were completelyionized. By way of example, an equivalent weight of phenol is equal tothe gram-molecular weight of phenol; an equivalent weight of catechol isequal to one-half the gram-molecular Weight of catechol.

The diaminopropanes that form reaction products whose use is included bythis invention may be illustrated by the generic formula:

the'diamines in which the long-chain,'aliphatic N-substituent of thesecondary amino grouping is an alkyl or alkenyl group containing atleast 12, and preferably from 'lZ'to 18' straight chain carbon atoms areconsidered to form especially effective addition agents. Examples of1,31'liaminopropanes which are considered to form cs pecially effectiveaddition agents for the purposes of this invention are the 3-dodecylandthe 3-hexadecylami-nopropylamines, and especially the 18 carbon 'alkyl-,all enyl-, and alkadienyl substituted 'l,3-diaminopropanes, such as the3octadecyl-, 3-octadecenyl-(3-oleyl), and 3-octadecadienylaminopropylamines. Although aliphatic hydrocarbonN-substituted 1,3-diaminopropanes are preferred, the invention includesphenolic reaction products derived from diamines in which theN-substituent of the secondary amino grouping is itself substituted withone or more groups that contain elements such as oxygen, sulfur,nitrogen, phosphorus or halogen and that do not interfere with theoil-solubility of the adduct. Representative examples of1,3-diaminopropanes containing such substituents are3-ricinoleylaminopropylamine and 3- (chlorostearyl)aminopropylamine.Mixtures of 1,3-di-, aminopropanes, such as are formed when thelong-chain, aliphatic N-substituent in the secondary amino grouping isderived from mixed fatty acids obtained from naturally occurring fatsand oils, form highly effective phenolic adducts Within the scope ofthis invention. In such instances the aliphatic N-substituent in'thesecondary amino groupi-ng will be a straight-chain, monov alenthydrocarbon radical containing from 8 to 20 carbon atoms. Examples ofsuch mixtures of 1,3-diaminopropanes are 3-tallowaminopropylamine,3-"soya-aminopropylamine, and 3- coco-aminopropylamine, where therespective N-substituents are mixed alkyl and unsaturated alkyl groupsderived from animal tallow -(C -C fatty acids, soybean (C C fatty acids,and coconut (Cg-C fatty acids.

The phenolic compounds that form adducts with the herein disclosedN-substituted 1,3-diaminopropanes include those which do not hinder theoil-solubility of the resulting reaction product. Thus, the inventionincludes, for example, reaction products of the discloseddiamines andmonohydric, dihydric tor polyhydric phenolic compounds, such as phenolitself, catechol, resorcinol, and hydroquinone. Especially preferredphenols are'the hydrocarbon substituted phenols, e'.g., those havingalkyl or aralkyl substitutents attached to the phenolic nucleus,specificexamples of which are iOI'thO-, meta-, and paracresol,

ortho-, meta-, and parabutylphenol, p-nonylphenol, 3,5-

diamylphenol, 3-methyl-5-propylphenol, 3-methyl-5-butylphenol,3,5-diethylphenol, 3-et hyl-5-propylphenol, m-propylphenol,m-butylphenol, m-amylphenol, and p-octy-lphenol,bis-(2-hydroxy-3,S-diamylphenyl)sulfide, mono-, bis-, andtris-alpha-methylbenzylphenols, alpha-phenylethylcatechols, variousbis-(hydroxyalkylphenyl)'-alkanes, representative of which are2,2-bis-(4-hydroxy-5-methylpheny1)propane,1,1-bis-(2-hydroxy3,S-dimethylphenyl)- isobutane, bis (2 hydroxy 3 tbutyl 5-methylphen-' yl)-methane, and1,1-bis-(2-hydroxy-3-t-butyl-5-methylm olecular weight) of mixed m-alkylphenols were faddistillation or the like.

.At (a) is shown the probable formula for the reaction compounds inwhich the phenolic nucleus is substituted: with hydnocarbon substituentsare preferred, the invention also includes the use of phenols containingnon-hydrocarbon substituents such as nitro, chloro, bromo, amino andlike groups, specific examples ofgsuch phenols being pnitro phenol, pamino phenol, and 'penta-chloro phenol. I

Commercial mixtures of phenols are also suitable for the purposes ofthis invention. Such mixtures may be those recoveredby treatmentofindustrial wastes, by treatment of petroleum refinery process waters, orfromv coal tar Although the exact nature of thdadducts herein describedhas not been definitelyascertained, it is thought likely that theseadducts partake of the nature of sub- 7 stituted ammonium'salts.Examples aregiven below of the formulae structure thought to beinvolved.

'xo-l Fonicnicnt-nn, V

product of equimolar proportions of a diamine and .a monohydric phenoliccompound. At (b) is shown'the probable formula for the reaction productof 0.5 mol diamine with 1 mol of monohydric phenolic compound. At (6) isshown the probable formula for the reaction prod uct of equimolarproportions of a'diamine and a'dihydric phenolic compound; Intheseformulae XO- represents the negative ion of a monohydric phenol,

represents the negative ion of adihydric phenol, and R is as definedabove.

' The preparation of the reaction products whose use is included by thisinvention, described in general, supra, is further illustrated by thefollowing specific examples.

'EXAMPLEI Approximately 7.5 grams (0.05 combining grammixed and reactedwith 20.0 grams (0.05 combining gram- 1 molecular weight) of3-"tallow-aminopropylamine. The reaction occurred spontaneously and wascompletejin'less than about fifteen minutes. .A temperature change inthe I a the course \of the reaction. To insure completion ofthe reactionmixture of from 2910 35C. was noted during 7 t stituents contained notmore than 4 carbon atoms each,

and in which'the total alkyl carbon atoms was between 3" and 5, togetherwith substantial proportions of;4-vand 5- indanol. The mixture containedapproximately 95 percent phenyl)-ethane. Other phenols, the use of whichis inf phenols. More particularly, in addition to indanols, the

mixed phenols of this example contained m-alkyl phenols such as:3-methyl-5-ethylphenol, 3-methyl-5-propy1phe no],B-methyIeS-butyIphenOl, 3,5-diethy1phenol, 3,-ethyl-5- 4-indanolS-indanol 15 3-methy1-5-ethylphenol 10 n-Propylphenols (meta and para)5-10 Mixed meta-substituted phenols of type indicatecL- 45-50 Thephysical properties of a typical sample of the mixed phenols were asfollows:

Average molecular weight, approx 140450 Apparent specific gravity at /20C 1.03 Boiling range (ASTM D-850):

-1.B.P C 240 1% C 242 5% C 245 50% C 250 95% C 270 DP C 280 Vaporpressure at 20 C mm. Hg 0.01 Viscosity at 20 C cps. approx 70 Solubilityin water at 20 C percent by wt 0.08 Solubility of Water in 20 C do 5Refractive index at C 1.543 Behavior on cooling-sets to glass or cloudsbelow C Average weight per gal. at 60 F lb 8.63 Flash point (open cup) F250 The 3-tallow-aminopropylamine employed in this example containedapproximately 80 percent diamines and was made up of a mixture of3-fatty alkyland alkenylaminopropylamines. The mixture had a theoreticalmolecular weight of 320, a combining weight of approximately 400, and amelting range of approximately 44 to 48 C. The fatty alkyl and alkenylsubstituents of the mixed diamines were derived from animal tallow fattyacids. Accordingly, the 3-tallow-aminopropylamine containedpredominantly 3-oleylarninopropylamine (3- octadecenylaminopropylamine),together with lesser proportions of 3-hexadecyland3-octadecylaminopropylamines, and small amounts of S-rnyristyland3-linoleylarninopropylamines.

The adduct prepared according to the foregoing procedure was abrown-colored liquid material having the following analysis: Nitrogen,percent, 5.64.

EXAMPLE II The adduct formed by reaction of mixed m-alkyl phenols and3-tallow"-aminopropylamine in the ratio of 0.5 mol diarnine perequivalent Weight of phenols (1:2 mol ratio) was prepared by reacting15.0 grams (0.1 combining gram-molecular weight) of the mixed m-alkylphenols described in Example I with 20 grams (0.05 combininggram-molecular weight) of the 3-tallow-aminopropylamine definedinExample I. The reaction proceeded spontaneously, a temperature changefrom 29 to 41 C. being noted during the course of the reaction. After nofurther temperature change was noted, the mixture was heated to 110 C.in order to insure completion of the reaction. The product of thisreaction was a brown-colored liquid material having the followinganalysis: Nitrogen, percent, 4.57.

EXAMPLE III The reaction product formed by reacting the3-tallow-aminopropylamine of Example I with mixedalphamethylbenzylphenols in a ratio of 1 mol of diamine per equivalentweight of phenols (1:1 mol ratio) was prepared by admixing 11.6 grams(0.05 combining grammolecular weight) mixed alpha-methylbenzylphenolsand 20.0 grams (0.05 combining gram-molecular weight) of3-"tallow-aminopropylamine. Again the reaction pro ceeded spontaneously,the temperature changing during the course of the reaction (less than 15minutes) from 27 to 35 C. The mixture was then heated to 110 C.

The mixed alpha-methylbenzylphenols employed in the reaction were anapproximately percent pure mixture of substituted phenols containingpredominantly ortho- (alpha-methylbenzyl)phenol, bis-( alphamethylbenzyl)- phenol, and tris-(alpha-methylbenzyl)phenol in therespective approximate Weight proportions of 12 percent, 2 percent and36.7 percent, the balance of the over-all mixture being made up ofhigher substituted phenols.

The reaction product resulting from the foregoing reaction Was abrown-colored liquid material having the following analysis: Nitrogen,percent, 5.49.

EXAMPLE IV Another adduct was formed by reacting the3-tallowaminopropylamine of Example I with bis-(2-hydroxy-3,5-diamylphenyl)sulfide in a ratio of 1 mol of diamine per equivalentweight of the bis-phenol sulfide (2:1 mol ratio). The reaction wascarried out by admixing 20.0 grams (0.05 combining gram-molecularweight) of 3- "talloW-aminopropylamine with 12.5 grams (0.025 combininggram-molecular weight) of the bis-phenol sulfide.

The materials reacted spontaneously, a temperature change of 25 to 35 C.being observed. When no further temperature change occurred, the mixturewas heated to C.

The product of the foregoing reaction was a viscous, brown-coloredliquid material having the following analysis:

Nitrogen, percent 4.66 Sulfur, percent 2.92

EXAMPLE V Another adduct was prepared by reacting3-tallowaminopropylamine and para-octylphenol in a ratio of 1 mol ofdiamine per equivalent weight of phenol (1;1 mol ratio). According tothis example 8.0 grams (0.02 combining gram-molecular weight) of the3-tallowaminopropylamine of Example I were admixed with 4.13 grams (0.02mol) of p-octylphenol. The temperature of the reaction mixture changedfrom 25 to 29 C. during the reaction, which proceeded spontaneously. Themixture was heated to 110 C. after no further spontaneous temperaturechange was noted, in order to insure completion of the reaction. Theproduct of the reaction was a tan-colored liquid material having thefollowing analysis: Nitrogen, percent, 5.61.

EXAMPLE VI A further adduct was formed by reacting3-laurylaminopropylamine and mixed m-alkyl phenols in a ratio of 1 molof diamine per equivalent Weight of m-alkyl phenols 1:1 mol ratio). Inthis example 6.06 grams (0.02 mol) of B-laurylaminopropylamine wereadmixed with 3.00 grams 0.02 combining gram-molecular Weight) of themixed m-alkyl phenols of Example I. The materials reacted spontaneously,a temperature change of 28 to 20 C. being noted. At the conclusion ofthe spontaneous reaction period, the mixture was heated to 110 C. toinsure driving the reaction to completion. The product of the foregoingreaction was a browncolored liquid material having the followinganalysis: Nitrogen, percent, 7.68.

EXAMPLE VII An additional adduct Was prepared by reacting 3-(2-ethylhexyl)aminopropylamine and mixed rn-alkyl phenols in a ratio of 1mol of amine per equivalent weight of phenols (1:1 mol ratio). In thisreaction 9.32 grams (0.05 mol) of 3-(2-ethylhexyl)aminopropylamine wereadmixed with 7.50 grams (0.05 combining gram-molecular weight) ofthe'mixed m-alkyl phenols referred to in Example I. The reactionproceeded spontaneously, a temperature change of from 26,to 48 (3. beingnoted, with heat to 100 C. being added thereafter. The product of thisreaction was abrown-colored liquid material having the followinganalysis: Nitrogen, percent, 8.96.

EXAMPLE VIII trogen, percent, 6.32.

The foregoing examples indicate the manner and ease of preparation ofthe adducts whose use is included by this invention, and also describedspecific embodiments.

of said adducts. Other adducts whose use is included by the inventioncan be prepared similarly as above by reaction in the indicatedproportions of other herein disclosed 1,3-diaminopropanes with theforegoing phenols, or with other members of the herein disclosed classof phenols.

The addition of very small amounts of the reaction products of theabove-described type to blended distillate fuel oils containing bothstraight run and catalytically cracked components has been found toprovide a marked improvement in the sludging-tendencies of the oils.Naturally, the various adducts of the herein disclosed class do notpossess'exactly identical effectiveness,'and the most advantageousconcentration for each such adduct will depend to some extent upon theparticular adduct used. Also, the minimum effective inhibitorconcentration may vary somewhat according to the specific nature of themixed fuel oil. In general, however, thehereinrdisclosed reactionproducts are useful in concentrations of as little as about 0.005percent to about 1.0 percent by weight of the composition. Majorimprovement of the sludging characteristics of mixed fuel oils isusually obtainable at storage temperatures, utilizing concentratedsolutions a of the. additivesrin solvents that have a high solubility.for the additives and that do not adversely affect the stability 'of theoil. Examples of such concentrated slu-, tions are to 75 weight percent,e.g., 50 percent, solutions offthe' "reaction .product' or equimolarproportions or 3-ftallow" aminopropylamine and p-octylphenol in solventssuchas kerosene, benzene, toluene, hexane, methyl isobutyl ketone, andmethyl ethyl keton e. V v v i v As indicated, the class of distillatefuel oils to which this invention is applicable includes mixtures ofstraight run and catalytically cracked distillate fuel oils such as areused for domestic'heating and' for some industrial heating purposes,typical of whichare the so-called No. 2 fuel oils, i.e., distillate oilsboiling withinthe range of about 350. to 750 F. and having a minimumAPI.

gravity of about26. V a

'The problem of stabilization of such oilsis unique and exists, onlywhen a catalytically,cracked'fueloil dis tillate and a straight run fueloil distillate are combined in such proportions as'to cause asubstantial, deleterious eifect of the kind previously described; .;The,invention is important when the ratio of thevolurne of the catalyticallycracked to the straight run oil is Within the range of about 9:1 andabout 1:9., It is especially-advantageous when applied tomixed oilscontainingthese oils in a volume ratio within the range of 4:1' and 1:4;

The utility of the herein disclosed class of sludge inhibiting adductsof long-chain, aliphatic N substituted 1,3-diaminopropanes andphenols'has been demonstrated by subjecting samples of Va blendofcatalytically cracked 1 and straight run fuel'oil distillates containingvarious concentrations of adducts representative of the class in cludedby the invention to'a standard accelerated sta-. bility test. The testsamples Weremade up by adding the desired concentration of each additionagent to be tested directly to separate samples of the blendedffuel byincorporation therein of from about 0.01 to about 0.05

percent by weight of the herein disclosed class of reaction products.Nevertheless, in some cases it may be advantageous to add as much asabout 0.1 percent by weight of the adducts. In very unusual cases it maybe found desirable to add as much as'about 1.0 percent by weight of theadducts.

The addition agents whose use is included by this invention may beincorporated in the mixed fuel oils in any suitable manner. Thus, theadducts may be formed in situ in the oil, they may be added, per'se,directly-to the mixed fuel oil, or they may be added in the form ofconcentrates, either immediately after formation of the mixture ofdistillate fuel oils, or afterthe mixture has been stored for asubstantial period of time. Alterna tively, the sludge inhibitingaddition agents of this invention may be formed in situ in, or added perse or in the form of'concentrated solutions to, either the straight runor the catalytically cracked fuel oil distillate, prior to blending ofthe components to form a mixed fuel oil. Suitable concentratescontaining the sludge inhibiting adducts of this invention comprise, forexample, mineral oil solutions or dispersions containing from about 10to 75 percent, and preferably from about 25 to percent, activeingredient. Where the concentrate is in the form of a dispersion, it maybe desirable to heat the dispersion and/or the oil that is to beinhibited, e.g., to a temperature between 100 F. and 140 F., in orderrtofacilitate blending. An alternate practice involves blending Gravity,API 33.5 Viscosity, SUS, 100 F. 34.5 Color, NPA 1.5+ Pour point, F. 15Flash point, F. a 168 Carbon residue, Conradson, on 10% bottoms 0.38Neutralization value, acid No. 0.12

Distillation: I

7 Initial boiling point, F. 360

End boiling point, 7 F. 630 Bromine No. 11.7 Olefins, wt. percent 15.1Aromatics, vol. percent 21.9 Aniline point F. 129 Ash, oxide, wt.percent 0.01,

oil whichhad the following physical properties:

' The stability test referred to was carried out on the 7 mixed fuel oilcompositions by heating 600-grarn samples of the fuel oil compositionsfor periods ranging from 16 'to '64 hoursat 2l0 F. in loosely stoppcred,one quart clear glass bottles. Following the heating periods the testsamples were cooled to room temperature and filteredby suction'thi'oughtared, medium porosity fritted glass 'Goooh-type crucibles. The sludgein each crucible. was washed with heptane.

sludge adhering to the inside of the bottles was obtained 1 Completeremoval of the obtainable with the Examples I to V1, inclusive, are setforth in Table A below:

Table A Sludge, ing/600 g. Oil

After After After After After 16Hrs. 24H1's. 40 Hrs. 48Hrs. 64Hrs.

1. Blend A1:1:1 (Vol) Blend of West Texas Straight Run,

South Louisiana Straight Run, and Fluid Catalytically Cracked N0. 2 FuelOil Distillate 8. 3 30.2 69.6 81. 2 99. 6 2. Blend A plus 0.02 Wt.Percent Reaction Product of Mixed Alkylphenols and3-"'lollotWeminopropylamine, 1:1 Mel Ratio (Example I Product) 2.3 0. 90. 4 0.7 0. 4 3. Blend Aplus 0.05 ft. Percent Reaction Product of MixedAl tvlphenols and 3-Tallow"-aminopropylan1ine, 1:1 M01 Ratio (Example IProduct) 2.0 4. Blend A plus 0.02 Wt. Percent R Alkvlphcnols and3-Tallow Ratio (Example If Product) 1. 7 1. 2 3. 1. 7 0- 2 5. Blend Aplus 0.05 Wt. Percent Reaction Product of h xed Alkylphenols andS-Tallow-aminopropylamine, 2:1 Mol Ratio (Example II Product) 3. 2 6.Blend A plus 0.02 Wt. Percent Reaction Product of Mixeda-Methvlbenzylphenols and 3-"Tallow-aminopropylamine,

1:1 Mol Ratio (Example III Product) 0. 6 7. Blend A plus 0.02 Wt.Percent Reaction of Bis(2hydroxy-3,5-

diamylphenyl) sulfide and 3-"Tallow"-arninopropylaminc,

1:2 M01 Ratio (Example 1V Product) O. 8. Blend A plus 0.02 Wt. PercentReaction Product of p-Octylphenol and 3-Tallo\v-eminopropylarnine, 1:1Mol Ratio (Example V Product) 3. 3 9. Blend A plus 0.02 Wt. PercentReaction Product of Mixed Alltylphenols and 3-Laurylarninopropylarnine,1:1 Mol Ratio (Example VI Product)" 0. 4

Compositions 2 to 9, inclusive, in the foregoing table are specificembodiments of the invention. Comparison of the results set forth in thetable for these compositions With those obtained from blank Compositions1 indicates the major improvement obtainable with the addition agentsincluded by this invention. The foregoing results are considered typicalof the preferred additives of this invention. Similar results areobtainable with other reaction products of the herein disclosed class,specific examples of which are the reaction products of 3dodecylaminopropylamine, 3 tetradecylaminopropylamine,3-hcxadecy1aminopropylamine, 3-octadecylarninopropylamine, and 3-octadecenylarninopropylamine with phenol, catechol, resorcinol,hydroquinone, cresol, bis-(2-hydroxy-3-t-butyl-5 methylphenyDmcthane,1,1- bis-(2-hydroxy-3-t-butyl-5-methylphenyl)ethane,3-methyl-S-propylphenol, 3-methyl-5-butylphenol, 3,5-diethylphenol,3-ethyl-5-propylphenol, m-propylphenol, m-butylphenol, andm-arnylphenol, in ratios of 0.5 and 1 mol of diamine per equivalentweight of phenol. Other specific examples of addition agents Whose useis included by the invention are reaction products of the foregoingphenols in the ratios indicated with mixed fatty alkylandalkenylaminopropylamines such as 3-coco-arninopropylamine and3-soya"-aminopropylamine. Other examples of fuel oil compositionsincluded by the invention are mixtures of catalytically cracked andstraight run No. 2 fuel oil distillates, Where the volume ratio ofcracked to straight run oil is from 9:1 to 1:9, e.g., 4:1, 2:1, 1:1,1:2, 1:4, containing from 0.005 to 1.0 Weight percent, e.g., 0.01, 0.02,0.03, 0.04, 0.05 percent, of the above-named reaction products.

In order to demonstrate the importance of the use of the hereindisclosed class of 1,3-diaminopropanes in forming the reaction productsdisclosed herein, the results obtained by incorporating the reactionproducts of Example VII and VIII in the blended fuel oil have beenprepared by reaction of a low molecular Weight alkyl-substitutedaminopropylamine and a phenol.

Table B After 24 hrs. (1) Blend A (see Table A) 30.2 (2) Blend A plus0.02 wt. percent reaction product of mixed alkylphenols and3-(2-ethylhexyl) aminopropylamine, 1:1 mol ratio (Example VII)- 27.1 (3)Blend A plus 0.02 Wt. percent reaction product of mixed alkylphenols and3-(2-cthylhexyl) aminopropylamine, 2:1 mol ratio (Example V-I'II) 27.8(4) Blend A plus 0.02 wt. percent reaction product ofbis-(2-hydroxy-3,S-dia-mylphenyl)sulfide and3-isopropylaminopropylamine, 1:2 mol ratlo 64.8

In the foregoing table, Compositions 2 and 3 are specific embodiments ofthe invention. As indicated by the results obtained with thesecompositions and set forth in the foregoing table, reaction productsinvolving the use of C aliphatic N-substituted aminopropylaminesrepresent the threshold of utility insofar as sludge inhibition in mixedcatalytically cracked and straight run distillate fuel oils isconcerned.

If desired, the stable fuel oil compositions of this invention maycontain in addition to the additives disclosed herein other improvementagents, such as for example, oxidation inhibitors, filash point controlagents, corrosion inhibitors, anti-foam agents, ignition qualityimprovers, combustion improvers and other additives adapted to improvethe oils in one or more respects.

Although, as indicated in the preliminary discussion of the problem ofsludging in blended fuel oils in relation to the problem ofdeterioration of other petroleum oils, the former is entirely distinct,the multifunctional reaction products of the herein disclosed inventionhave also been found to have utility in approximately the sameconcentrations that are used in fuel oils in inhibiting gum formation ingasolines. The utility of the herein disclosed reaction products ingasoline was determined by subjecting samples of a gasoline consistingof ther- '1 l mally cracked distillate to standard oxidation stabilitytest ASTM D525-49. According to this test the gasoline sample isintroduced into an oxidation bomb and oxygen is added to a pressure ofabout 100 psi. The charged bomb is placed in a boiling Water bath andthe gas pressure in V the bomb is recorded. The end of the inductionperiod, i.e,, the point at which rapid absorption of the oxygen by thegasoline takes place, is the time when a sharp drop in pressure (atleast 2 psi. in minutes) occurs.

The results obtained by the foregoing test are indicated in Table Cbelow:

' 12 reactants being from about 0.5 to about 1 mol of th1,3-diaminopropane per equivalent weight of phenolic 1 compound, saidsmall amount being sufficient to inhibit sludge deposition from saidmixture of oils.

2. The fuel oil composition of claim l'wherein said small amountisbetween-about 0.005 andfabcut 1.0,percent by weight of said mixture ofoils.

3. The fuel oil composition of claim .1 where the' phenolic compound isalkyl-substituted and monohydric and whereRis alkenyl;

V 4. A fuel oil composition comprising a major proper- 7 tion of amixture of straight run and catalytically cracked distillate fuel 'oilstending to deposit sludge and a small amount or the reaction productformed by the substantially spontaneous reaction of (a) mixed m-alkylphenols whose alkyl substituents contain not more than 4. carbon atomseach and whose total alkyl carbon atoms per molecule is from 3 to 5, and(b) mixed 3-alkyland 3-alkenylaminopropylamines whose alkyl and 'alkenylsubstituents contain from 14 to 18 carbon atoms, the 11101 ratio ofreactants being from about 1 to 2 mols of phenols per Comparison of theinduction period for Compositions 3 and 4 of Table C with the inductionperiod for Com-- position 2 (the blank gasoline plus a known commercialgum inhibitor) indicates the remarkable improvement obtainable with thereaction products 'of this invention.

Although applicants inhibitors have proved effective to inhibit bothsludging in blended fueloilsand gum formation in gasoline, the problemsinvolved in the respective instances are considered chemically andphysically nonanalogous. For example, the dissimilar natures of theproblems of inhibiting gum in gasolnes and sludging in blended fuel oilswere demonstrated by subjecting another sample of the above-identifiedgasoline and a sample of a 50/50 by volume blend of Eastern Venezuelastraight run and fluid catalytically cracked No. 2 fuel oil distillateshaving a marked tendency 'to deposit sludge, respectively, to ASTM testD525-49. In

the former instance a marked drop in the oxygen pres-' sure of the bombwas observed after only '97 minutes. In the instance of the blended fueloil no marked drop in the oxygen pressure had occurred after 161.5hours, at which time the test was discontinued.

It will be apparent to those skilled in the art that many variations ofthe invention may be resorted to without departing from the spiritthereof. Accordingly, only such limitations should be imposed as areindicated in the claims appended hereto.

This application is a division of our copcnding application Serial No.449,491, filed August 12, 1954, and now U.S. Patent 2,942,028.

We claim:

1. A fuel oil composition comprising a major proportion of a mixture ofstraight run and catalytically cracked distillate fuel oils tending todeposit sludge and a small amount of the reaction product formed by thesubstantially spontaneous reaction of a phenolic compound that will nothinder the oil-solubility of said reaction product and that is selectedfrom the group consisting of unsubstituted and mono-, di-, andtri-substituted monoand dihydric phenols whose substituents are selectedfrom the group consisting of alkyl and aryl-substituted alkyl radicalscontaining 1 to 9 carbon atoms,

and oil-soluble bis-phenolic sulfides and alkanes derived from suchphenols, and a 1,3-diaminopropane of the general formula:

molofaminopropylamines, said small amount being suffi cient to inhibitsludge'deposition from saidimixture of oils. 1

-5. A fuel oil composition comprising a major proportion of a mixture ofstraight run and catalytically cracked distillate fuel oils tending todeposit sludge and a small amount of the reaction product formed by thesubstantially spontaneous reaction of about equirnolar proportions ofmixed alpha-methylbenzylphenols and mixed 3-alkyland3-alkenylaminopropylamines whose' alkyl and alkenyl substituents containfrom 14 to 18 carbon atoms, said small amount being sufiicient toinhibit sludge deposition from said mixture of oils.

'6. A fuel oil composition comprising a major proportion of a mixture ofstraight run and catalytically cracked distillate fuel oils tending todeposit sludgefand a small amount of the reaction product formed by theI substantially spontaneous reaction of bis-(2-hydroxy-3,5-.

diamylphenyl)sulfide and mixed 3'-alkyland *3-alkenylaminopropylamineswhose alkyl and alkenylsubstituents contain from 14 to 18 carbon atoms,the mol ratio of reactants being about 1:2, said small amount'beingsuffi- 'cient to inhibit sludge deposition from said mixture of oils. Vr

7. A fuel oil'cornposition. comprising a major propor:

tion of a mixture of straight run and catalytically cracked distillatefuel oils tending to deposit sludge and a small] amount of the reactionproduct formed by the substan tially spontaneous reaction of aboutequimolar proportions of ,p-octylphenol and mixed 3-alkyland3-alkenylaminopropylamines whose alkyl and alkenyl substituents containfrom 14 to 18 carbon atoms, said small amount being sufficient to.inhibit sludge deposition from said mixture of oils.

-8. A fuel oil composition comprising a major proportion of 'a mixtureof straight run and catalytically cracked distillate fueloils tending todepositsludge and j a small amount of the reaction product formed by thesubstantially spontaneous reaction of about .equimolar proportions of3-laurylaminopropylamine' and mixed m-alkyl phenols whose alkylsubstituents contain not more than 4 carbon atoms each and whose totalalkyl carbon atoms per molecule is from 3 .105, said small amount beingsufficient to inhibit sludge deposition fro said mixture of oils.

9. A fuel composition comprising major proportion I of a normallyunstable liquid hydrocarbon fuel and a small amount, sufiicient tostabiilzesaidfueljof the reaction product formed by the substantiallyspontaneous reaction of a phenolic compound that will not hinder theoil-solubility of said reaction product and that is selected from thegroup consisting of unsubstituted and mono-, diand tri-substitutedmonoand dihydric phenols whose substituents are selected from the groupconsist-.

ing of alkyl and aryl-substituted alkyl radicals contains" 13 ing 1 to 9carbon atoms, and oil-soluble bis-phenolic sulfidies and alkanes derivedfrom such phenols, and a 1,3-diaminopropane of the general formula:

R HI1TCH2CH2-CH3-NH5; Where R is an aliphatic hydrocarbon radicalselected from the group consisting of alkyl, alkenyl, and alkadienylcontaining 8 to 30 carbon atoms, the ratio of reactants being in therange of about 0.5 to about 1 mol of the w 1,3-diaminopropane perequivalent weight of the phenolic compound.

References Cited in the file of this patent OTHER REFERENCES Sernon Aug.7, 1934 Scheumann Sept. 23, 1941 Chenicek Dec. 22, 1942 Fareri et al.Aug. 11, 1959 Schnaith et al. Sept. 29, 1959 FOREIGN PATENTS GreatBritain Sept. 2, 1933

1. A FUEL COMPOSITION COMPRISING A MAJOR PROPORTION OF A MIXTURE OFSTRAIGHT RUN AND CATALYTICALLY CRACKED DISTILLATE FUEL OILS TENDING TODEPOSIT SLUDGE AND A SMALL AMOUNT OF THE REACTION PRODUCT FORMED BY THESUBSTANTIALLY SPONTANEOUS REACTION OF A PHENOLIC COMPOUND THAT WILL NOTHINDER THE OIL-SOLUBILITY OF SAID REACTION PRODUCT AND THAT IS SELECTEDFROM THE GROUP CONSISTING OF UNSUBSTITUTED AND MONO-, DI-, ANDTRI-SUBSTITUTED MONO- AND DIHYDRIC PHENOLS WHOSE SUBSTITUENTS ARESELECTED FROM THE GROUP CONSISTING OF ALKYL AND ARYL-SUBSTITUTED ALKYLRADICALS CONTAINING 1 TO 9 CARBON ATOMS, AND OIL-SOLUBLE BIS-PHENOLICSULFIDES AND ALKANES DERIVED FROM SUCH PHENOLS, AND A 1,3-DIAMINOPROPANEOF THE GENERAL FORMULA: